Application of the singlet reference interaction site model to the primitive model double layer

Abstract

2011) Application of the singlet reference interaction site model to the primitive model double layer,The Singlet Reference Interaction Site Model (SRISM) is employed to a structural study of the planar electric double layer using the primitive model of the double layer in which the solvent is implicit, being characterized by a dielectric constant, the ions are represented by charged hard spheres, while the electrode is a uniformly charged flat surface. The primitive model double layer has the advantage that simulation results encompassing a wide range of physical states are available for comparison purposes. The predicted results are compared with some recent simulations and an earlier simulation for an extreme case. The SRISM with closures based on the hypernetted chain show the most promise of the closures considered here. Although the SRISM results are not perfect, the accuracy of SRISM with the best closures is often comparable to the modified Poisson-Boltzmann theory, while the density functional theory seems more accurate for the extreme cases. The SRSIM has the advantage that explict water molecules can be included and solutions can be obtained for high densities. Furthermore, since molecular ions can be treated, SRISM seems suitable for the study of ionic liquids.

Application of the SRISM approach to the study of the capacitance of the double layer of a high density primitive model electrolyte

“…We reviewed the SRISM theory in detail in our previous paper [1] and there is little need to repeat this discussion. Two closures were examined, the hypernetted chain (HNC) and Kovalenko-Hirata (KH) closures.…”

“…In a recent paper [1], two of us together with Bhuiyan (WBH) applied the Singlet Reference Interaction Site Model (SRISM), using both the hypernetted chain (HNC) and Kovalenko-Hirata (KH) closures, to the study of density profiles of the double layer formed by a restricted primitive model (RPM) at low electrolyte densities and concluded that the HNC closure was preferable. However, that study was an introductory one whose purpose was to apply and test our programs to the previously studied systems.…”